CN102844271A - Fire-resistant filler powder, adhesive material, and method for producing fire-resistant filler powder - Google Patents
Fire-resistant filler powder, adhesive material, and method for producing fire-resistant filler powder Download PDFInfo
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- CN102844271A CN102844271A CN2011800193278A CN201180019327A CN102844271A CN 102844271 A CN102844271 A CN 102844271A CN 2011800193278 A CN2011800193278 A CN 2011800193278A CN 201180019327 A CN201180019327 A CN 201180019327A CN 102844271 A CN102844271 A CN 102844271A
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- against fire
- resistivity against
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1003—Pure inorganic mixtures
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Abstract
Disclosed is a fire-resistant filler powder such that willemite and gahnite are deposited in the same particle.
Description
Technical field
The present invention relates to the method for manufacture of resistivity against fire filler powder, sealing material and resistivity against fire filler powder, and relate to the method for manufacture of resistivity against fire filler powder, sealing material and resistivity against fire filler powder of sealing of the electronic unit such as sealing, piezoelectric vibrator package, IC package of display unit such as suitable plasm display panel (below be called PDP), OLED display, field-emitter display (below be called FED), fluorescent display tube (below be called VFD).
Background technology
As sealing material, use the composite powder material that contains glass powder and resistivity against fire filler powder.Compare with the resene tackiness agent, the chemical durability of sealing material and excellent heat resistance, and be suitable for guaranteeing resistance to air loss.
As the glass powder that uses in the sealing material, use PbO-B
2O
3Be glass (referenced patent document 1 etc.).But from the viewpoint of environment, requirement is removed PbO in being made up of glass, thereby has developed Bi
2O
3-B
2O
3Be glass.And, disclose in patent documentation 2 grades: Bi
2O
3-B
2O
3The fusing point that is glass is low, and has and PbO-B
2O
3It is the same chemical durability of glass.
On the other hand, the resistivity against fire filler powder of using in the sealing material is added for the reduction that realizes thermal expansivity, the raising of physical strength, as its material, has brought into use the lead titanate of low bulk etc.But, same with glass powder, require to remove PbO by in the forming of resistivity against fire filler powder.Therefore, as the resistivity against fire filler powder, willemite, trichroite, tindioxide, beta-eucryptite, mullite, silica, β-quartz solid solution, aluminium titanates, zircon etc. are studied.Wherein, the expansion of willemite is low, and and Bi
2O
3-B
2O
3The flexibility that is glass well (is difficult for making Bi during sealing
2O
3-B
2O
3Be the glass devitrification), thereby receive publicity (referenced patent document 3, non-patent literature 1).
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication sho 63-315536 communique
Patent documentation 2: japanese kokai publication hei 8-59294 communique
Patent documentation 3: japanese kokai publication hei 4-114930 communique
Non-patent literature
Non-patent literature 1:E.N.Bunting, " Phase equilibtia in the system SiO
2-ZnO-Al
2O
3", J.Res.NAT.Bur.Stand., 11,725,1933
Summary of the invention
Though willemite expands low, to compare with other resistivity against fire filler powder, the effect that improves the physical strength that seals the position is low.When the physical strength at sealing position was low, breakage took place because of mechanical impact etc. in sealing position easily, thereby was difficult to keep the resistance to air loss of display unit etc.
In addition, willemite is generally made through solid reaction process.Making through solid reaction process under the situation of willemite, accomplishing, need under high temperature (particularly being more than 1440 ℃), calcine raw material in order to make solid state reaction.Compared with the solid state reaction temperature when low in calcining temperature, part of raw materials is in unreacted state easily.If the raw material of remained unreacted in the sealing material is separated out unwanted crystallization easily, thereby poor sealing is taken place easily in the glass when then sealing.On the other hand, the fusing point of willemite is about 1510 ℃, near above-mentioned solid state reaction temperature (with reference to non-patent literature 1).Therefore, compare with the solid state reaction temperature when too high in calcining temperature, thermal welding takes place in calcine easily during calcining, and the crush efficiency of calcine significantly reduces as a result, and the manufacturing cost of sealing material raises.
Therefore; Technical task of the present invention is; Through inventing out low bulk, HS and can carrying out the resistivity against fire filler powder of solid state reaction at low temperatures and cheapization that method of manufacture realizes sealing material, prevent simultaneously because of the breakage at sealing position and the poor sealing that unreacted raw material is caused.
The inventor has carried out unremitting effort, and the result finds, has separated out willemite and the main crystalline resistivity against fire filler powder of zinc spinel conduct through use, can solve above-mentioned technical task, and it is proposed as the present invention.That is, resistivity against fire filler powder of the present invention is characterised in that, in same particle, has separated out willemite and zinc spinel.
In same particle, separate out under the situation of willemite and zinc spinel, the situation that is merely willemite with main crystallization phases is compared, and the effect of the physical strength raising at sealing position is strengthened.As a result, prevent to seal the breakage at position easily, thereby keep the resistance to air loss of display unit etc. easily.In addition, through separating out of willemite, can also enjoy the effect that thermal expansivity is reduced effectively.
In addition, through the generation of zinc spinel, can promote the generation of willemite, therefore can reduce calcining temperature, the result makes calcine be difficult for taking place thermal welding, thereby improves the manufacturing efficient of resistivity against fire filler powder.
The second, resistivity against fire filler powder of the present invention is characterised in that the ratio of willemite and zinc spinel is 99: 1～70: 30 with molar ratio computing.Like this, can when keeping the effect that makes the thermal expansivity reduction, improve the physical strength at sealing position.
The 3rd, resistivity against fire filler powder of the present invention is characterised in that, as composition, in mole %, contains ZnO 60～79.9%, SiO
220～39.9%, Al
2O
30.1～10%.Like this, make willemite and zinc spinel reach optimum proportion easily, when keeping the effect that thermal expansivity is reduced, improve the physical strength at sealing position easily.
The 4th, resistivity against fire filler powder of the present invention is characterised in that, is prepared from through solid reaction process.Solid reaction process is following method: at first according to the raw materials such as composition allotment oxide compound of expectation, after it is calcined, the calcine fragmentation of gained, pulverizing, classification are prepared the resistivity against fire filler powder.Utilize this method, need not carry out the fusion of raw material, therefore can reduce the manufacturing cost of resistivity against fire filler powder.
The 5th, sealing material of the present invention is the sealing material that contains glass powder and resistivity against fire filler powder, it is characterized in that, as the resistivity against fire filler powder, contains above-mentioned resistivity against fire filler powder.
The 6th, sealing material of the present invention is characterised in that the content of resistivity against fire filler powder is 0.1～70 volume %.Like this, make easily the thermal expansivity of sealing material with by the matched coefficients of thermal expansion of sealer, and can improve the physical strength of sealing material.
The 7th, sealing material of the present invention is characterised in that glass powder is Bi
2O
3-B
2O
3Be glass.Bi
2O
3-B
2O
3The fusing point that is glass is low, and thermostability, water tolerance are good, therefore has the bubble-tight character that seals at low temperatures easily and guarantee display unit etc. easily.In addition, Bi
2O
3-B
2O
3The flexibility that is glass and resistivity against fire filler powder of the present invention is good.Need to prove that "～be glass " is meant that containing the composition shown clearly is 30 moles more than the %, is preferably 40 moles more than the %, 50 moles of glass (down with) more than the % more preferably as neccessary composition and its total amount.
The 8th, sealing material of the present invention is characterised in that, contains also that to be selected from trichroite, zircon, beta-eucryptite, silica glass, aluminum oxide, mullite, aluminum oxide-silica be that in the pottery one or more are as the resistivity against fire filler powder.
The 9th, sealing material of the present invention is characterised in that, also contains mineral dye.
The tenth, sealing material of the present invention is characterised in that, does not contain PbO in fact.Like this, can satisfy in recent years environmental requirement." do not contain PbO in fact " here, and be meant that the content of the PbO in the sealing material is the situation below the 1000ppm (quality).
The 11, the method for manufacture of resistivity against fire filler powder of the present invention is characterised in that, according to containing ZnO 60～79.9%, SiO in mole %
220～39.9%, Al
2O
30.1 after～10% composition has been allocated raw material, willemite and zinc spinel are separated out through solid reaction process.
Description of drawings
Fig. 1 is that expression is surveyed the synoptic diagram of the softening temperature of periodic sealing material with macroscopic view (マ Network ロ) type DTA device.
Fig. 2 is the diagrammatic cross-section of a mode of the dull and stereotyped one-piece type vapor pipe of expression.
Fig. 3 is the diagrammatic cross-section of a mode of the dull and stereotyped one-piece type vapor pipe of expression.
Embodiment
In the resistivity against fire filler powder of the present invention, the ratio of willemite and zinc spinel is preferably willemite with molar ratio computing: zinc spinel=99: 1～70: 30,95: 5～80: 20 is preferably 90: 10～85: 15 especially.When the ratio of zinc spinel is too much, reduce the deleterious of thermal expansivity, and temperature of reaction high temperatureization, the manufacturing cost of resistivity against fire filler powder raises easily.On the other hand, when the ratio of zinc spinel is very few, improve the deleterious of physical strength.
Resistivity against fire filler powder of the present invention as composition, in mole %, preferably contains ZnO60～79.9% (preferred 63～70%), SiO
220～39.9% (preferred 28～35%), Al
2O
30.1～10%.Masterbatch (バ Star チ) during preparation resistivity against fire filler powder is formed, and in mole %, preferably also contains ZnO 60～79.9%, SiO
220～39.9%, Al
2O
30.1～10%.ZnO and SiO
2It is the crystalline constituent.Al
2O
3Being the crystalline constituent, and playing a role as reaction promotor, is the composition that reduces calcining temperature.Need to prove, if consider the effect as reaction promotor, then Al
2O
3Content be preferably that 0.1 mole of % is above, 1 mole of % is above, be preferably 3 moles more than the % especially.Al
2O
3Content when being less than 0.1 mole of %, be difficult to bring into play effect as reaction promotor.On the other hand, Al
2O
3Content when too much, be difficult to generate willemite.
Resistivity against fire filler powder of the present invention preferably is prepared from through solid reaction process.Utilize this method, need not carry out the fusion of raw material, therefore can reduce the manufacturing cost of resistivity against fire filler powder.In addition, preferably before calcining, raw material is pulverized mixing.Like this, between the raw material when receiving mechanical impact the state with micropowder mix, therefore, the specific surface area of raw material increases, the result can promote solid state reaction.In addition, can also shorten calcination time like this.Need to prove that calcining temperature is preferably the temperature that calcine thermal welding does not take place and the crystallization of expectation is fully separated out, and particularly is preferably 1400～1460 ℃.
In the sealing material of the present invention, the median size D of resistivity against fire filler powder
50Be preferably below the 20 μ m, be preferably 2～15 μ m especially.Like this, can not improve the manufacturing cost (pulverizing cost, classification cost) of resistivity against fire filler powder, and reduce seal thickness easily.Need to prove, in order to enjoy the effect that the resistivity against fire filler powder is brought effectively, the median size D of resistivity against fire filler powder
50Be preferably more than the 0.5 μ m.Here, " median size D
50" being meant the value of utilizing laser diffractometry to measure, expression utilizes laser diffractometry to survey in the cumulative grain-size distribution curve of periodic volume reference, is 50% o'clock particle diameter from begin to accumulate its cumulative amount than small-particle one side.
In the sealing material of the present invention, the maximum particle diameter D of resistivity against fire filler
MaxBe preferably below the 100 μ m, be preferably 10～75 μ m especially.Like this, can not improve the manufacturing cost of sealing material, and reduce seal thickness easily.Here, " median size D
Max" being meant the value of utilizing laser diffractometry to measure, expression utilizes laser diffractometry to survey in the cumulative grain-size distribution curve of periodic volume reference, is 99% o'clock particle diameter from begin to accumulate its cumulative amount than small-particle one side.
Sealing material of the present invention contains glass powder and resistivity against fire filler powder, it is characterized in that, as the resistivity against fire filler powder, contains above-mentioned resistivity against fire filler powder.In the sealing material of the present invention, the content of resistivity against fire filler powder is preferably 0.1～70 volume %, 15～50 volume %, is preferably 20～40 volume % especially.The content of resistivity against fire filler powder is during more than 70 volume %, and the content of glass powder reduces relatively, so the flowability of sealing material reduces, and sealing intensity reduces easily as a result.On the other hand, when the content of resistivity against fire filler powder is less than 0.1 volume %, the deleterious of resistivity against fire filler powder.Need to prove; In the sealing material of the present invention, the content of resistivity against fire filler powder of the present invention (main crystallization phases be the resistivity against fire filler powder of willemite and zinc spinel) is preferably 0.1～70 volume %, 15～50 volume %, is preferably 20～40 volume % especially.
As glass powder, the glass powder that can use various glass to be.For example, consider preferred Bi from the aspect of lower melting point characteristic
2O
3-B
2O
3Be glass, V
2O
5-P
2O
5Be glass, SnO-P
2O
5Be glass, consider, preferred especially Bi from thermostability, water-proof aspect
2O
3-B
2O
3Be glass.
For Bi
2O
3-B
2O
3Be glass, form that the mole % so that following oxide compound converts preferably contains Bi as glass
2O
315～50%, B
2O
315～50%, ZnO 0～45% (preferred 1～40%).Like this, can take into account thermostability and lower melting point characteristic with high level.In addition, in order to improve thermostability, preferably add 0.1 mole of % above BaO, Fe
2O
3, among the CuO one or more.
In the sealing material of the present invention, the median size D of glass powder
50Preferably less than 15 μ m, 0.5～10 μ m, be preferably 1～5 μ m especially.The median size D of glass powder
50During less than 15 μ m, the softening temperature of glass powder reduces, and the flowability of sealing material improves.
Sealing material of the present invention can contain also that to be selected from trichroite, zircon, beta-eucryptite, silica glass, aluminum oxide, mullite, aluminum oxide-silica be that in the pottery one or more are as the resistivity against fire filler powder.These resistivity against fire filler powder are useful from regulating thermal expansivity with viewpoint mobile and the raising physical strength.In addition, the content of these resistivity against fire filler powder is preferably 0～30 volume % in total amount, is preferably 0～10 volume % especially.
Sealing material of the present invention preferably also contains mineral dye.Like this, can reduce the bad order at sealing position.The content of mineral dye is preferably 0～10 volume %, 0.1～5 volume %, is preferably 0.5～3 volume % especially.The content of mineral dye is during more than 10 volume %, and the dissolve in amount of mineral dye in glass increases during sealing, so the thermostability of sealing material is impaired easily.As mineral dye, preferred Cu is that oxide compound, Fe are that oxide compound, Cr are that oxide compound, Mn are oxide compound and their spinelle type composite oxides.
In the sealing material of the present invention, the median size D of mineral dye
50Be preferably 0.01～5 μ m, 0.5～5 μ m, be preferably 1～3 μ m especially.The median size D of mineral dye
50During greater than 5 μ m, be difficult to make mineral dye to be distributed to equably in the sealing material, partial poor sealing may take place.On the other hand, the median size D of mineral dye
50During less than 0.01 μ m, mineral dye is added in the glass easily during sealing, so the thermostability of sealing material is impaired easily.
In order to make the seal thickness homogenization, sealing material of the present invention can also contain the following spun glass of 10 volume %, granulated glass sphere, silica beads, resin bead etc. as spacer.
In the sealing material of the present invention, thermal expansivity is preferably 80 * 10
-7/ ℃ below, be preferably 75 * 10 especially
-7/ ℃ below.Like this, can reduce, therefore, prevent easily to seal that stress rupture takes place at the position and the bubble-tight situation of damaging display unit etc. by residual stress in sealer or the sealing position.Here, " thermal expansivity " is meant the value of in 30～300 ℃ TR, utilizing push-down MEASURING THE THERMAL EXPANSION COEFFICIENT (TMA) device to measure.
In the sealing material of the present invention, softening temperature is preferably below 475 ℃, is preferably especially below 460 ℃.Like this, can improve the flowability of sealing material.Here, " softening temperature " is meant the value of utilizing differential calorimetric analysis (DTA) device to measure, can utilize macroscopical type DTA device, in atmosphere, 10 ℃/minute of heat-up rates, begin from room temperature to measure under the condition such as mensuration.Need to prove that under the situation of macroscopical type DTA, the temperature (Ts) of the 4th flex point shown in Figure 1 is equivalent to softening temperature.
In the sealing material of the present invention, Tc is preferably more than 550 ℃, more than 570 ℃, be preferably more than 600 ℃ especially.Like this, in calcination process (polishing (グ レ one ズ) operation, degreasing (debinder) operation) and secondary clacining operation (sealing process), be difficult for separating out crystallization in the glass, guarantee the resistance to air loss of display unit etc. easily.Here, " Tc " is meant the crystallization peak temperature that utilizes the DTA device to measure to obtain, and can utilize macroscopical type DTA device, in atmosphere, 10 ℃/minute of heat-up rates, begin from room temperature to measure under the condition such as mensuration.
Sealing material of the present invention can supply in use with pulverulence, but as if evenly mediating with carrier and processing thickener, then is easy to handle, thereby preferred.Carrier generally includes solvent and resin.Resin adds from the purpose of the viscosity of regulating thickener.In addition, based on needs, also can add surfactant, thickener etc.The thickener of making uses coating machines such as divider, screen process press to be applied to by on the surface of sealer.
As resin, can use propenoate (vinyl resin), TKK 021, polyethyleneglycol derivative, Nitrocellulose, polyvinyltoluene, polymerized thylene carbonate ethyl ester, methacrylic ester etc.Particularly propenoate, Nitrocellulose are because pyrolytic is good preferably.
As solvent; Can use N, N '-N (DMF), α-terpinol, higher alcohols, gamma-butyrolactone (γ-BL), tetraline, acetate of butyl carbitol, ETHYLE ACETATE, Isoamyl Acetate FCC, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetic ester, benzylalcohol, toluene, 3-methoxyl group-3-methyl butanol, water, triethylene glycol monomethyl ether, triglyme, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, Texacar PC, methyl-sulphoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-etc.α-terpinol particularly is because viscosity is high and also good and preferred to the solvability of resin etc.
Sealing material of the present invention preferably sinters predetermined shape into and uses after the panelized.In the sealing of the vapor pipe of PDP etc., using is shaped is processed as cyclic flat board (pressed glass material/glass sintering body/glass shaping body).Be formed with the patchhole that is used to insert vapor pipe on the flat board, vapor pipe be inserted into this insert in the hole, make the position contraposition of venting hole of leading section and the panel of vapor pipe, and fix with clip etc.Then, in the secondary clacining operation, make dull and stereotyped softening, thereby vapor pipe is installed on the panel.If sealing material of the present invention is processed into flat board; Then when the installation of vapor pipe; Easily vapor pipe is connected on the exhaust equipment, and can reduces the inclination of vapor pipe, and can easily install in the luminous power of keeping PDP etc., to guarantee the mode of airtight safety.
Dull and stereotyped make through thermal treatment repeatedly.At first, in sealing material, add resin, solvent and prepare slurry.Then, this slurry is put in the prilling granulator such as spray-drier, made particle.At this moment, particle carries out drying making under the temperature of solvent evaporates (about 100～200 ℃).And then, the particle of making is put in the mould that is designed to predetermined size, the dry type press forming is a ring-type then, makes press body.Then, in heat treatment furnaces such as conveyor type sintering oven, make resin residual in this press body decompose volatilization, then sintering in addition under the temperature about the softening temperature of sealing material.Like this, can make the flat board of predetermined shape.In addition, sintering number can be set at repeatedly.Thus, dull and stereotyped intensity improves, and prevents dull and stereotyped damaged, destruction etc. easily.
Sealing material of the present invention, thereby preferably on the basis of panelized, further the leading section of the vapor pipe after being installed to hole enlargement uses with the form of the one-piece type vapor pipe of flat board.Like this, need not be that starting point is carried out vapor pipe and dull and stereotyped contraposition with the venting hole, can simplify the fitting operation of vapor pipe.
When making dull and stereotyped one-piece type vapor pipe, at first, need heat-treat making under the leading section state of contact of dull and stereotyped and vapor pipe, thereby in advance with the leading section of panel splice to vapor pipe.At this moment, preferably utilize anchor clamps that vapor pipe is fixed, inserted dull and stereotyped and carry out heat-treating methods to the vapor pipe of this state.The anchor clamps that are used for fixing vapor pipe preferably do not make the material of dull and stereotyped generation thermal welding, for example carbon jig etc.In addition, vapor pipe carries out, for example carries out getting final product in about 5～10 minutes with the short period of time with the dull and stereotyped softening temperature that is bonded on sealing material is neighbouring.
As vapor pipe, preferably contain the SiO of the alkalimetal oxide of predetermined amount
2-Al
2O
3-B
2O
3Be glass, the FE-2 that preferred especially Nippon Electric Glass Co., Ltd makes.The thermal expansivity of this vapor pipe is 85 * 10
-7/ ℃, heat resisting temperature is 550 ℃, size for example is external diameter 5mm, internal diameter 3.5mm.In addition, if the leading section of vapor pipe is carried out hole enlargement, then can improve autonomous stability.At this moment, the leading section of vapor pipe is preferably toroidal or flange shape.As the method that the leading section of vapor pipe is carried out hole enlargement, can adopt the whole bag of tricks.Particularly make leading section rotation time of vapor pipe use gas burner to heat and use several kinds of anchor clamps to be processed into the method for predetermined shape, because mass productivity is good and preferred.Fig. 2 illustrates an example of the dull and stereotyped one-piece type vapor pipe of this formation.That is, Fig. 2 is the sectional view of dull and stereotyped one-piece type vapor pipe, and the leading section of vapor pipe 1 has carried out hole enlargement, and engages at the leading section of the panel side of vapor pipe and to have dull and stereotyped 2.
As the one-piece type vapor pipe of flat board; Preferred following structure: the leading section of the vapor pipe after hole enlargement is equipped with dull and stereotyped and the HMP flat board; And, flat board is installed in the leading section side of the vapor pipe after the hole enlargement, compare with flat board the HMP flat board is installed in the rearward end side.Should constitute if adopt, then vapor pipe had been installed to last time such as panel, increase when only vapor pipe being installed, therefore install perpendicular to panel easily with the contact area of panel etc.In addition, when being fixed to flat board on the vapor pipe, it is dull and stereotyped between flat board and anchor clamps, to dispose HMP, does not therefore need special anchor clamps, and the result can simplify the manufacturing process of dull and stereotyped one-piece type vapor pipe.
In the above-mentioned dull and stereotyped one-piece type vapor pipe; Preferably have the formation that the periphery of the leading section of dull and stereotyped and vapor pipe engages, have more preferably that flat board only engages with the periphery of the leading section of vapor pipe and not with the front end face of the leading section of vapor pipe, the formation that promptly engages with face that panel etc. joins.Prevent to flow into the situation of venting hole like this, easily at the constituent of vacuum exhaust operation middle plateform.In addition, directly do not engage and be fixed on the vapor pipe, then in the secondary clacining operation, can the HMP plate part carried out pressure seal to vapor pipe under by clip fixed state through flat board with vapor pipe if HMP is dull and stereotyped, thereby preferably.Fig. 3 illustrates an example of the dull and stereotyped one-piece type vapor pipe of this formation.That is, Fig. 3 is the sectional view of dull and stereotyped one-piece type vapor pipe, and the leading section of vapor pipe 1 has carried out hole enlargement, and engaging at the leading section of the periphery side of the flange portion 1a of vapor pipe 1 has dull and stereotyped 2.On the other hand, HMP dull and stereotyped 3 not with the periphery side engagement of vapor pipe 1.In addition, dull and stereotyped 2 are installed in the leading section side of flange portion 1a, and HMP dull and stereotyped 3 is compared the rearward end side that is installed in flange portion 1a with dull and stereotyped 2.
Here, dull and stereotyped as above-mentioned HMP, ST-4, FN-13 that preferred Nippon Electric Glass Co., Ltd makes.In material is under the situation of glass, and the making method of HMP flat board is the same with the making method of above-mentioned flat board.In addition, dull and stereotyped as HMP, also can use pottery, metal etc.
Below, based on embodiment the present invention is described at length.
Table 1 illustrates the embodiment (sample No.1～4) and the comparative example (sample No.5～7) of resistivity against fire filler powder of the present invention.
[table 1]
Make the resistivity against fire filler powder in the table through solid reaction process.At first, allocate the raw material of various oxide compounds, and use ball mill to pulverize and mixed 10 minutes～3 hours according to the composition in the table.This ground mixt is packed in the alumina crucible, and calcining is 20 hours under the calcining temperature in table.At last, with pulverizing with ball mill after the fragmentation of gained calcine, and carry out classification, obtain median size D with 250 purpose sieves
50It is the resistivity against fire filler powder of 12 μ m.For each resistivity against fire filler, have or not calcine thermal welding, have or not the evaluation of unreacted raw material (being mainly ZnO).Its result is shown in table 1.
Can know by table 1, contain Al in the composition of sample No.1～4
2O
3, therefore separate out willemite and zinc spinel as main crystallization, even calcining temperature is 1420～1440 ℃, there is not unreacted reactant yet, solid state reaction is accomplished.On the other hand, do not contain Al in sample No.5,6 the composition
2O
3, therefore do not separate out zinc spinel, be under 1430 ℃ the situation in calcining temperature, residual have a unreacted raw material, in calcining temperature is under 1470 ℃ the situation, the thermal welding of calcine to take place, and is difficult to broken state and calcine is become.In addition, do not separate out willemite among the sample No.7, the weak effect that therefore thermal expansivity is reduced.
Table 2 illustrates Bi
2O
3-B
2O
3The glass that is glass is formed example and characteristic thereof.
[table 2]
The Bi shown in the preparation table 2 is described below
2O
3-B
2O
3Be glass.At first, prepare to form raw material such as the various oxide compounds of allotment, carbonate and the glass masterbatch that obtains, this glass masterbatch is packed in the platinum crucible, 1100 ℃ of following fusions 1 hour according to the glass in the table.Then, it is laminar to utilize water cooled rolls that melten glass is configured as.At last, after laminar glass pulverized with ball mill, carry out classification, obtain median size D with 200 purpose sieves
50It is the glass powder of 10 μ m.
Glass transition point and softening temperature are in air atmosphere, to utilize the DTA device to measure the value that obtains.In addition, begin to measure from room temperature, heat-up rate is set at 10 ℃/minute.
Thermal expansivity is to utilize the TMA device to measure the value that obtains.Measure TR and be set at 30～300 ℃.In addition, as measuring sample, use sintered compact with the glass powder of densification to be processed as predetermined shape and the sample that obtains.
Table 3 illustrates embodiment (Sample A～D) and the comparative example (sample E, F) of sealing material of the present invention.
[table 3]
Resistivity against fire filler powder shown in the table 1 is mixed according to the volume ratio shown in the table with the glass powder shown in the table 2, make each sample in the table thus.For each sample, carry out the evaluation of glass transition point, softening temperature, thermal expansivity and folding strength.Its result is shown in table 3.
Glass transition point and softening temperature are in air atmosphere, to utilize the DTA device to measure the value that obtains.In addition, begin to measure from room temperature, heat-up rate is set at 10 ℃/minute.
Thermal expansivity is to utilize the TMA device to measure the value that obtains.Measure TR and be set at 30～300 ℃.Need to prove,, use sintered compact with the sealing material of densification to be processed into predetermined shape and the sample that obtains as measuring sample.
Folding strength is according to JIS R1601: the three point bending test of the bending strength test method defined of fine ceramics is measured the value that obtains.
Can know that by table 3 thermal expansivity of Sample A～D is low, and folding strength is high.On the other hand, the folding strength of sample E is lower than sample A～D.Need to prove that the manufacturing cost of the resistivity against fire filler powder of sample E is high, think that therefore its manufacturing cost is higher than sample A～D.In addition, the thermal expansivity of sample F is higher than sample A～D.
Industrial applicability
Resistivity against fire filler of the present invention and use the sealing material of this resistivity against fire filler to be fit between the core of sealing, (3) magnetic head of the electronic units such as sealing, (2) piezoelectric vibrator package, IC package of display unit such as (1) PDP, OLED display, FED, VFD or the sealing of the means of illumination such as the organic EL illumination in sealing, (5) of solar cells such as the sealing of core and slide block, (4) silicon solar cell, dye-sensitized solar cell.
Claims (11)
1. a resistivity against fire filler powder is characterized in that,
Willemite and zinc spinel in same particle, have been separated out.
2. resistivity against fire filler powder as claimed in claim 1 is characterized in that,
The ratio of willemite and zinc spinel is 99: 1～70: 30 with molar ratio computing.
3. according to claim 1 or claim 2 resistivity against fire filler powder is characterized in that,
As composition,, contain ZnO 60～79.9%, SiO in mole %
220～39.9%, A1
2O
30.1～10%.
4. like each described resistivity against fire filler powder in the claim 1～3, it is characterized in that,
Be prepared from through solid reaction process.
5. a sealing material contains glass powder and resistivity against fire filler powder, it is characterized in that,
The resistivity against fire filler powder is each described resistivity against fire filler powder in the claim 1～4.
6. sealing material as claimed in claim 5 is characterized in that,
The content of resistivity against fire filler powder is 0.1～70 volume %.
7. like claim 5 or 6 described sealing materials, it is characterized in that,
Glass powder is Bi
2O
3-B
2O
3Be glass.
8. like each described sealing material in the claim 5～7, it is characterized in that,
Contain also that to be selected from trichroite, zircon, beta-eucryptite, silica glass, aluminum oxide, mullite, aluminum oxide-silica be that in the pottery one or more are as the resistivity against fire filler powder.
9. like each described sealing material in the claim 5～8, it is characterized in that,
Also contain mineral dye.
10. like each described sealing material in the claim 5～9, it is characterized in that,
Do not contain PbO in fact.
11. the method for manufacture of a resistivity against fire filler powder is characterized in that,
According to containing ZnO 60～79.9%, SiO in mole %
220～39.9%, Al
2O
30.1 after～10% composition has been allocated raw material, willemite and zinc spinel are separated out through solid reaction process.
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|---|---|---|---|
| JP2010-098440 | 2010-04-22 | ||
| JP2010098440A JP5605748B2 (en) | 2010-04-22 | 2010-04-22 | Refractory filler powder, sealing material and method for producing refractory filler powder |
| PCT/JP2011/058941 WO2011132554A1 (en) | 2010-04-22 | 2011-04-08 | Fire-resistant filler powder, adhesive material, and method for producing fire-resistant filler powder |
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| JP (1) | JP5605748B2 (en) |
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| CN110740980A (en) * | 2017-08-29 | 2020-01-31 | 日本电气硝子株式会社 | Filler powder and method for producing same |
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| JP5605748B2 (en) * | 2010-04-22 | 2014-10-15 | 日本電気硝子株式会社 | Refractory filler powder, sealing material and method for producing refractory filler powder |
| US8871664B2 (en) * | 2010-05-10 | 2014-10-28 | Nippon Electric Glass Co., Ltd. | Refractory filler, sealing material using same, and manufacturing method for refractory filler |
| JP5779922B2 (en) * | 2011-03-16 | 2015-09-16 | 日本電気硝子株式会社 | Refractory filler and sealing material using the same |
| KR102522821B1 (en) * | 2017-09-04 | 2023-04-18 | 니폰 덴키 가라스 가부시키가이샤 | Method and apparatus for manufacturing glass articles |
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|---|---|---|---|---|
| CN1379742A (en) * | 1999-10-18 | 2002-11-13 | 康宁股份有限公司 | Transparent glass-ceramics based on alpha-and beta-willemite |
| JP2009155200A (en) * | 2007-12-06 | 2009-07-16 | Nippon Electric Glass Co Ltd | Sealing material |
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| JPH07102982B2 (en) | 1987-06-16 | 1995-11-08 | 日本電気硝子株式会社 | Frit for low temperature sealing |
| JP2968985B2 (en) * | 1990-09-05 | 1999-11-02 | 日本電気硝子株式会社 | Low melting point sealing composition |
| JPH06171980A (en) * | 1992-12-04 | 1994-06-21 | Sumitomo Metal Mining Co Ltd | Composition for substrate fired at low temperature |
| JP3424219B2 (en) | 1994-08-17 | 2003-07-07 | 日本電気硝子株式会社 | Low melting point sealing composition |
| KR20090037915A (en) * | 2006-10-24 | 2009-04-16 | 니폰 덴키 가라스 가부시키가이샤 | Bismuth-base glass composition and bismuth-base material |
| JP5605748B2 (en) * | 2010-04-22 | 2014-10-15 | 日本電気硝子株式会社 | Refractory filler powder, sealing material and method for producing refractory filler powder |
| US8871664B2 (en) * | 2010-05-10 | 2014-10-28 | Nippon Electric Glass Co., Ltd. | Refractory filler, sealing material using same, and manufacturing method for refractory filler |
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- 2010-04-22 JP JP2010098440A patent/JP5605748B2/en active Active
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- 2011-04-08 CN CN201180019327.8A patent/CN102844271B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379742A (en) * | 1999-10-18 | 2002-11-13 | 康宁股份有限公司 | Transparent glass-ceramics based on alpha-and beta-willemite |
| JP2009155200A (en) * | 2007-12-06 | 2009-07-16 | Nippon Electric Glass Co Ltd | Sealing material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110740980A (en) * | 2017-08-29 | 2020-01-31 | 日本电气硝子株式会社 | Filler powder and method for producing same |
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| KR20120131220A (en) | 2012-12-04 |
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| WO2011132554A1 (en) | 2011-10-27 |
| KR101441598B1 (en) | 2014-09-22 |
| JP2011225402A (en) | 2011-11-10 |
| US8853111B2 (en) | 2014-10-07 |
| CN102844271B (en) | 2016-02-03 |
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